US2542544A - Process of producing polyaryl methane dyes of the rosaniline type - Google Patents
Process of producing polyaryl methane dyes of the rosaniline type Download PDFInfo
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- US2542544A US2542544A US32988A US3298848A US2542544A US 2542544 A US2542544 A US 2542544A US 32988 A US32988 A US 32988A US 3298848 A US3298848 A US 3298848A US 2542544 A US2542544 A US 2542544A
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- United States
- Prior art keywords
- rosaniline
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- aniline
- producing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/18—Preparation by oxidation
Definitions
- This invention relates to a process of producing' triarylmethane dyestuffs. More specifically, the invention relates to an improved process of catalytzcally oxidizing leuco triarylmethane dyes
- Many triarylmethane dyes for example, those of the rosaniline type, are commercially made by the oxidation was effected with commercial oxidants such as arsenic acids.
- this process was eventually superseded by one using mononitrobenzene because of the practical impossibiliof course, batch processes and required a number of steps in separating the dye from the reaction Side reactions also resulted which made the method dlstinctly unattractive.
- the best catalyst is obtained by reducing sodium' metavanadate with acetic anhydride.
- Ammonium metavana'date may also be used and vanadium compounds suchas vanadium pentoxide it is somewhat inferior to the All the reactants may reaction vessel separately, but preferably in the one of its practical advantages.
- the amount of excess amine is not critical, but
- EXAM LE 1 Preparation of the catalyst described in the following Stoichi'ometrical equivalents of sodium hydroxide are added to a solution of ammonium added to acetic anhydride in amounts approximately ten times that of the sodium metavana- "date. The resulting slurry is stirred and heated C., a brown solution being gradually wh ch reacts violently with the acetic Finally, a gray precipitate is formed to from five to ten times its volume produced anhydride. and is added of aniline.
- EXAMPLE 2 20 parts of iron free anhydroformaldehyde aniline are slurried in 150 parts of aniline and 6 parts of 23 Be hydrochloric acid.
- the oxidized dyestuff in the form of its hydrochloride is then recovered in the usual manner, involving the steam stripping of the excess of amine under controlled pH conditions, collecting fractions of the dyestuif soluble at different pH yalues, precipitating the base and collecting by filtration.
- Example 3 The procedure of Example 2 substituting ammonium metavanadate for the catalyst described in Example 1. A good yield of oxidizing dyestufi is obtained, but does not approach the theoretical as closely as when the preferred catalyst is used. The quality of the product is also slightly inferior.
- EXAMPLE 4 i 4 mixture of 300 parts aniline and '70 cc. of concentrated C. P. hydrochloric acid is heated to 135140 C. After dehydration, the temperature is lowered to 100 C. and 20.5 parts of para toluidine added. 0.15 part or the vanadium catalyst is prepared as described in Example 1 and washed into the charge with 16 parts of aniline. The. temperature of the charge is kept at 110- 118 C.-and air introduced through an Ace dispersion tube. Oxidation is stopped after 24 hrs. and the melt is stzam stripped, extracted with dilute hydrochloric acid, and the product salted gut.. "-A very crystalline fuchsine is obtained.
- EXAMPLE 6 r 12 parts or leuco para fuchsine are slurried in 300 parts of aniline and 60 parts of hydro-. chloric acid. This mixture is dehydrated by heating at C. for 4 hours. The temperature is then lower. d to 110 C. and 01 part of catalyst is added. With mild agitation, dry air is bubbled through the charge by means of a porous gas dispersion tube at such a rate that a fine layer of foam covers the charge. The tempera: ture is maintained at 110-112 C. until color formation reaches a maximum (about 24 hours). The charge is then steam-distilled to remove excess aniline and the para-iuchsine extracted from the stripped material in the usual manner.
- a process of producing polyamino polyarylmethane dyestuffs of the rosaniline type which comprises oxidizing a dispersion leuco triamino triarylmethane in excess aryl amine by, gaseous oxygen in the presence of a catalyst selected from the group consisting of ammonium metavanadate and the reaction product obtained by heating sodium metavanadate and acetic anhydride to a temperature above 100 C.
- a process of producing polyamino polyarylmethane dyestufis of the rosaniline type which comprises oxidizing a dispersion of diamino diarylmethane in excess aryl amine by gaseous oxygen in the presence of a catalyst selected from the group consisting of ammonium metavanadate and the reaction product obtained byheating sodium metavanadate and acetic anhydride to a temperature above 100 C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Feb. 20, 1951 2,542,544 ICE PROCESS OF PRODUCING POLYARYL METH- ANE DYES OF THE ROSANILINE TYPE Serge A. Loukomsky, Bound Brook, and Guy &
Herrick, Middlesex, N. J. Company, Ne
yanamid ration of Maine assignors to American w York,
N. Y., a corpo- No Drawing. Application June 14, 1948, Serial No. 32,988
5' Claims. (01. 260391) This invention relates to a process of producing' triarylmethane dyestuffs. More specifically, the invention relates to an improved process of catalytzcally oxidizing leuco triarylmethane dyes Many triarylmethane dyes, for example, those of the rosaniline type, are commercially made by the oxidation was effected with commercial oxidants such as arsenic acids. However, this process was eventually superseded by one using mononitrobenzene because of the practical impossibiliof course, batch processes and required a number of steps in separating the dye from the reaction Side reactions also resulted which made the method dlstinctly unattractive.
tages of the process using commercial oxidizer, but the yields obtained did not result in the adop tion of these methods by industry.
are associated with an excess of the amines used in the production of the polyphenylmethane compound.
While the various vanadium catalysts and ticular catalysts with which the preferred form of. the present invention deals.
The best catalyst is obtained by reducing sodium' metavanadate with acetic anhydride.
Ammonium metavana'date may also be used and vanadium compounds suchas vanadium pentoxide it is somewhat inferior to the All the reactants may reaction vessel separately, but preferably in the one of its practical advantages.
The amount of excess amine is not critical, but
presented methane, t the vanadium catalyst.
Since one of the advantages of the used inthe present invene tion, but are used as chemical oxidizers and hence be introduced into the at least stoichiometrical proportions. When used as catalysts these compounds produce a very impure product.
Anhydrous reagents are required and the reaction should be carried out under conditions which result in the removal ofwater which may be formed. Unless adequate water removal is obtained, the advantages of the present invention are not fully realized.
The present invention will be greater detail in conjunction with examples. Parts are by weight;
EXAM LE 1 Preparation of the catalyst described in the following Stoichi'ometrical equivalents of sodium hydroxide are added to a solution of ammonium added to acetic anhydride in amounts approximately ten times that of the sodium metavana- "date. The resulting slurry is stirred and heated C., a brown solution being gradually wh ch reacts violently with the acetic Finally, a gray precipitate is formed to from five to ten times its volume produced anhydride. and is added of aniline. EXAMPLE 2 20 parts of iron free anhydroformaldehyde aniline are slurried in 150 parts of aniline and 6 parts of 23 Be hydrochloric acid. After stirring for some time an additional 64 parts of hydrochloric acid are added and the reaction mixture maintained at 70 C. overnight. The temperature is then'raised to 130 C. with stirring, the vapors'being allowed to escape, and. after about 5 hours 200 parts of aniline are added and the temperature brought down to 100-105 C.
0.15 part of the catalyst prepared as described in Example 1 is added and the reaction mixture aerated at 105-1l0 C. for from 15 to 1'? hours using dry air and maintaining thorough but not excessive agitation.
The oxidized dyestuff in the form of its hydrochloride is then recovered in the usual manner, involving the steam stripping of the excess of amine under controlled pH conditions, collecting fractions of the dyestuif soluble at different pH yalues, precipitating the base and collecting by filtration.
EXAMPLE 3 The procedure of Example 2 substituting ammonium metavanadate for the catalyst described in Example 1. A good yield of oxidizing dyestufi is obtained, but does not approach the theoretical as closely as when the preferred catalyst is used. The quality of the product is also slightly inferior.
EXAMPLE 4 i 4 mixture of 300 parts aniline and '70 cc. of concentrated C. P. hydrochloric acid is heated to 135140 C. After dehydration, the temperature is lowered to 100 C. and 20.5 parts of para toluidine added. 0.15 part or the vanadium catalyst is prepared as described in Example 1 and washed into the charge with 16 parts of aniline. The. temperature of the charge is kept at 110- 118 C.-and air introduced through an Ace dispersion tube. Oxidation is stopped after 24 hrs. and the melt is stzam stripped, extracted with dilute hydrochloric acid, and the product salted gut.. "-A very crystalline fuchsine is obtained.
4 EXAMPLE A mixture of 300 parts aniline and '70 cc. of concentrated C. P. hydrochloric acid is heated to 135-140? C. After dehydration, the temp;rature is loweredto 100C. and 23 parts of m-xyilidine added. 015 part of the vanadium catalyst is prepared as described in Example 1 and washed into the charge with 16 parts of aniline. The temperature of thecharge is kept at -118 C. and air introduced through an Ace dispersion tube. Oxidation is stopped after 2 1 hours and the melt is steam stripped, extracted with dilute hydrochloric acid, and the product salted out. A very crystalline fuchsine is obtained.
EXAMPLE 6 r 12 parts or leuco para fuchsine are slurried in 300 parts of aniline and 60 parts of hydro-. chloric acid. This mixture is dehydrated by heating at C. for 4 hours. The temperature is then lower. d to 110 C. and 01 part of catalyst is added. With mild agitation, dry air is bubbled through the charge by means of a porous gas dispersion tube at such a rate that a fine layer of foam covers the charge. The tempera: ture is maintained at 110-112 C. until color formation reaches a maximum (about 24 hours). The charge is then steam-distilled to remove excess aniline and the para-iuchsine extracted from the stripped material in the usual manner.
We claim: v
1. A process of producing polyamino polyarylmethane dyestuffs of the rosaniline type which comprises oxidizing a dispersion leuco triamino triarylmethane in excess aryl amine by, gaseous oxygen in the presence of a catalyst selected from the group consisting of ammonium metavanadate and the reaction product obtained by heating sodium metavanadate and acetic anhydride to a temperature above 100 C.
2. A process of producing polyamino polyarylmethane dyestufis of the rosaniline type which comprises oxidizing a dispersion of diamino diarylmethane in excess aryl amine by gaseous oxygen in the presence of a catalyst selected from the group consisting of ammonium metavanadate and the reaction product obtained byheating sodium metavanadate and acetic anhydride to a temperature above 100 C.
3. A process according to claim 2 in which the aryl amine is aniline and the diamino diarylmethane is p-diamino diphenylmethane.
4.. A continuous process according to claim 3 in which the diamino diarylmethane is prepared in the reaction mixture by reacting anhydroformaldehyde aniline with an excess of aniline in the presence of a condensing agent.
5. A method according to claim 1 in which the leuco dyestufi is leuco para iuchsine.
SERGE A. LOUKOMSKY. GUY S. HERRICK.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS 1943. revised by Thorne et al'.),,pp. 193-495. h
Claims (1)
1. A PROCESS OF PRODUCING POLYAMINO POLYARYLMETHANE DYESTUFFS OF THE ROSANILINE TYPE WHICH COMPRISE OXIDIZING A DISPERSION OF THE LEUCO TRIAMINO TRIARYLMETHANE IN EXCESS ARYL AMINE BY GASEOUS OXYGEN IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF AMMONIUM METAVANADATE AND THE REACTION PRODCUTS OBTAINED BY HEATING SODIUM METAVANADATE AND ACETIC ANHYDRIDE TO A TEMPERATURE ABOVE 100* C.
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US32988A US2542544A (en) | 1948-06-14 | 1948-06-14 | Process of producing polyaryl methane dyes of the rosaniline type |
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US32988A US2542544A (en) | 1948-06-14 | 1948-06-14 | Process of producing polyaryl methane dyes of the rosaniline type |
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US2542544A true US2542544A (en) | 1951-02-20 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3884869A (en) * | 1974-01-08 | 1975-05-20 | American Cyanamid Co | Coloring system for thermosetting plastic compositions |
US4566999A (en) * | 1983-03-18 | 1986-01-28 | Hoechst Aktiengesellschaft | Process for the preparation of acid dyestuffs of low electrolyte content of the triphenylmethane series |
US5922085A (en) * | 1997-09-30 | 1999-07-13 | Basf Corporation | Preparation of a dye for coloring protein-based fibers and cellulose-based materials from the oxidation products of the manufacture of a triphenylmethane dye |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US471638A (en) * | 1892-03-29 | Benno homolka | ||
US1694057A (en) * | 1926-11-24 | 1928-12-04 | Cole Robert Mcfarlan | Process of making triphenylmethane dyes |
US1805925A (en) * | 1927-10-28 | 1931-05-19 | Gen Aniline Works Inc | Process for the oxidation of leuco compounds of the triaryl methane series |
-
1948
- 1948-06-14 US US32988A patent/US2542544A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US471638A (en) * | 1892-03-29 | Benno homolka | ||
US1694057A (en) * | 1926-11-24 | 1928-12-04 | Cole Robert Mcfarlan | Process of making triphenylmethane dyes |
US1805925A (en) * | 1927-10-28 | 1931-05-19 | Gen Aniline Works Inc | Process for the oxidation of leuco compounds of the triaryl methane series |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3884869A (en) * | 1974-01-08 | 1975-05-20 | American Cyanamid Co | Coloring system for thermosetting plastic compositions |
US4566999A (en) * | 1983-03-18 | 1986-01-28 | Hoechst Aktiengesellschaft | Process for the preparation of acid dyestuffs of low electrolyte content of the triphenylmethane series |
US5922085A (en) * | 1997-09-30 | 1999-07-13 | Basf Corporation | Preparation of a dye for coloring protein-based fibers and cellulose-based materials from the oxidation products of the manufacture of a triphenylmethane dye |
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